Activation of water on MnOx-nanocluster-modified rutile (110) and anatase (101) TiO2 and the role of cation reduction

dc.contributor.authorRhatigan, Stephen
dc.contributor.authorNolan, Michael
dc.contributor.funderScience Foundation Irelanden
dc.contributor.funderHorizon 2020en
dc.date.accessioned2019-10-23T04:24:51Z
dc.date.available2019-10-23T04:24:51Z
dc.date.issued2019-02-12
dc.description.abstractSurface modification of titania surfaces with dispersed metal oxide nanoclusters has the potential to enhance photocatalytic activity. These modifications can induce visible light absorption and suppress charge carrier recombination which are vital in improving the efficiency. We have studied heterostructures of Mn4O6 nanoclusters modifying the TiO2 rutile (110) and anatase (101) surfaces using density functional theory (DFT) corrected for on-site Coulomb interactions (DFT + U). Such studies typically focus on the pristine surface, free of the point defects and surface hydroxyls present in real surfaces. In our study we have considered partial hydroxylation of the rutile and anatase surfaces and the role of cation reduction, via oxygen vacancy formation, and how this impacts on a variety of properties governing the photocatalytic performance such as nanocluster adsorption, light absorption, charge separation, and reducibility. Our results indicate that the modifiers adsorb strongly at the surface and that modification extends light absorption into the visible range. MnOx-modified titania can show an off-stoichiometric ground state, through oxygen vacancy formation and cation reduction spontaneously, and both modified rutile and anatase are highly reducible with moderate energy costs. Manganese ions are therefore present in a mixture of oxidation states. Photoexcited electrons and holes localize at cluster metal and oxygen sites, respectively. The interaction of water at the modified surfaces depends on the stoichiometry and spontaneous dissociation to surface bound hydroxyls is favored in the presence of oxygen vacancies and reduced metal cations. Comparisons with bare TiO2 and other TiO2-based photocatalyst materials are presented throughout.en
dc.description.sponsorshipERA.Net for Materials Research and Innovation (M-ERA.Net 2); SFI (Grant Number SFI/16/M-ERA/3418 RATOCAT)en
dc.description.statusPeer revieweden
dc.description.versionPublished Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.articleid67en
dc.identifier.citationRhatigan, S. and Nolan, M. (2019) 'Activation of Water on MnOx-Nanocluster-Modified Rutile (110) and Anatase (101) TiO2 and the Role of Cation Reduction', Frontiers in Chemistry, 7, 67. (12pp.) DOI: 10.3389/fchem.2019.00067en
dc.identifier.doi10.3389/fchem.2019.00067en
dc.identifier.eissn2296-2646
dc.identifier.endpage12en
dc.identifier.journaltitleFrontiers in Chemistryen
dc.identifier.startpage1en
dc.identifier.urihttps://hdl.handle.net/10468/8827
dc.identifier.volume7en
dc.language.isoenen
dc.publisherFrontiers Media S.A.en
dc.relation.projectinfo:eu-repo/grantAgreement/SFI/SFI US Ireland R&D Partnership/14/US/E2915/IE/SusChEM: Using theory-driven design to tailor novel nanocomposite oxides for solar fuel production/en
dc.relation.projectinfo:eu-repo/grantAgreement/EC/H2020::ERA-NET-Cofund/685451/EU/ERA-NET for materials research and innovation/M-ERA.NET 2en
dc.relation.projectinfo:eu-repo/grantAgreement/EC/H2020::ERA-NET-Cofund/685451/EU/ERA-NET for materials research and innovation/M-ERA.NET 2en
dc.relation.urihttps://www.frontiersin.org/articles/10.3389/fchem.2019.00067/full
dc.rights©2019 Rhatigan and Nolan. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these termsen
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.subjectTiO2en
dc.subjectWater activationen
dc.subjectReductionen
dc.subjectOxygen vacanciesen
dc.subjectPhotocatalysisen
dc.titleActivation of water on MnOx-nanocluster-modified rutile (110) and anatase (101) TiO2 and the role of cation reductionen
dc.typeArticle (peer-reviewed)en
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